DE3102620A1 - HARDENABLE RESIN - Google Patents

Description

Henkel, Kern, Feuer & Hanzel Patent attorneys Registered Representatives

before the

European Patent Office

MöhlstraBe 37 D-8000 Munich 80

Tel .: 089 / 982085-87 Telex: 0529802 hnk! d Telegrams: ellipsoid

FP / M-14-172 Dr. F / sm

MITSUBISHI GAS CHEMICAL COMPANY, INCORPORATED Tokyo / Japan

Curable resin composition

130052/0472

description

The invention relates to a curable resin composition in the form of a mixture and / or pre-reaction product of (a) one polyfunctional cyanate ester, a prepolymer of this cyanate ester and / or a co-prepolymer of this cyanate ester with an amine (referred to as component (a)) with (b) a polyhydantoin resin (referred to as component (b)) and a curable resin composition in the form of a mixture and / or pre-reaction product of component (a), the component (b) and (c) a polyfunctional maleic acid imide, a prepolymer of this maleic acid imide and / or a Covorpolymerts-at this maleimide with a Amine (referred to as component (c)).

Polyhydantoin resins have good water resistance and are commercially available in lacquer form or film form. However, the resistance to solvents leaves something to be desired and heat resistance of these resins. In addition, they are not suitable for the production of composite structures. On the other hand, cyanate ester resins are poor in water resistance. To improve the cons Of the cyanate ester resins, cyanate ester / maleimide resins have also been developed. Their resistance to bending cracks however, it is too low to be used in lacquer form.

The invention was based on the object of developing a resin composition which, after curing, makes a cured resin more excellent Provides flex crack resistance and excellent adhesion to the substrate.

The invention thus provides a curable resin composition in the form of a mixture and / or pre-reaction product (A) at least one polyfunctional cyanate ester, prepolymer of this cyanate ester and / or co-prepolymer this cyanate ester with an amine, (b) a polyhydantoin resin and optionally (c) at least one polyfunctional

130052/0472

len maleic acid imide, prepolymer of this maleic acid imide and / or co-prepolymer of this maleimide with an amine.

When a resin composition according to the invention is cured, one obtains a cured resin of the desired properties.

A polyfunctional cyanate ester is a compound with at least two cyanate groups in its molecule to understand. The polyfunctional cyanate esters which can be used according to the invention can be expressed by the formula:

R ¹ -f 0 - C s N)

reproduce. In the formula, R stands for a radical containing an aromatic nucleus. This is to a residue of an aromatic hydrocarbon, namely of benzene, biphenyl or naphthalene, or a residue of a Compound in which at least two benzene rings have a

Bridge link of the formula: ο

ι -C-

wherein R ² and R ^3, which can be the same or different, each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or of the formulas

Il

-0-, -CH ₉ OCH ₅ -, -S-, -C-, -0-CO-, -S-, -S-, -0-PO

Il Il Il Il I

0 0 0 0 0

or -0-P-0-

I 0

130052/0472

are bound to each other. Optionally, the aromatic nucleus is represented by at least one alkyl group with 1 to 4 Carbon atom (s), an alkoxy group containing 1 to 4 carbon atoms (en) or a chlorine or bromine atom substituted. Furthermore, in the cyanate ester formula given, m an integer from 2 to 5. The cyanate group is always bonded directly to the aromatic nucleus.

Examples of polyfunctional cyanate esters are dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-dicyanatophenyl) propane, bis (4-cyanatophenyl) ether, Bis (4-cyanatophenyl thioether, bis (4-cyanatophenyl sulfone, Tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate. Bis (3-chloro-4-cyanatophenyl) methane, a cyanatonovolak resin derived from a novolak resin and / or a bisphenol type cyanatopolycarbonate oligomer derived from a bisphenol type polycarbonate oligomer. Other cyanate esters that can be used are from JA-PS 1928/1966, 4791/1969, 11712/1970 and 41112/1971 as well as JP-OS 63129/1976 known. As already indicated, mixtures of the specified cyanate esters can also be used according to the invention will.

Furthermore, prepolymers containing a sym-triazine ring formed by trimerizing the cyanate groups of the cyanate ester can be used with average molecular weights of at least 400 to a maximum of 6000 are used. Such Vorpolymerie * fee is obtained by polymerizing the above Cyanate ester in the presence of a catalyst, e.g. B. an acid, such as a mineral or Lewis acid, a base, such as sodium hydroxide, a sodium alcoholate or a tertiary Amine, or a salt such as sodium carbonate or lithium chloride.

130052/0472

The polyfunctional cyanate ester can be in the form of a mixture of the monomer and the prepolymer are used. For example, there are many commercially available ones derived from bisphenol A and a cyanogen halide and cyanate esters which can be used according to the invention in the form of mixtures of cyanate monomers and prepolymers.

Furthermore, as cyanate ester component, Covorpolymerisa-te of the cyanate ester and an amine are used. Examples of those used in the manufacture of such co-prepolymer Usable amines are m- or p-phenylenediamine, m- or p-xylylenediamine, 1,4- or 1,3-cyclohexanediamine, Hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis (4-aminophenyl) methane. Bis (4-aminophenyl) ether, bis (4-aminophenyl) sulfone, Bis (4-amino-3-methylphenyl) methane, bis (3-chloro-4-aminophenyl) methane. Bis (4-amino-3,5-dimethylphenyl) methane, bis (4-aminophenyl) cyclohexane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amino-3-methylphenyl) propane, 2,2-bis (3,5-dibromo-4-aminophenyl) propane. Bis (4-aminophenyl) pheny! Methane, 3,4-diaminophenyl-4'-aminophenyl methane and 1,1-bis (4-aminophenyl) -1 -pheny lethane.

According to the invention, a mixture of the prepolymer of the cyanate ester and the co-prepolymer can also be used as component (a) of the cyanate ester and an amine are used.

In the case of the polyhydantoin resins which can be used according to the invention it is a resin with a hydantoin ring in the main chain, especially a resin with recurring Units of the formula:

130052/0472

- y -

H ₂ C

Il c

C = O

where R stands for a radical R or an imide ring. Such polyhydantoin resins are commercially available.

The ratio of component (a) to component (b) is not critical, expediently it should be from 99: 1 to 1:99, preferably 95: 5 to 35:65.

By using component (c) with components (a) and (b), the heat resistance of the ultimately cured resin even further.

In the case of the polyfunctional ones which can be used according to the invention Maleimides are organic compounds with 2 or more maleimide groups that are derived from maleic anhydride and a polyamine, and are represented by the following general formula:

play back. In the formula: R is a 2- to 5-valent aromatic or alicyclic organic group;

X and X, which may be the same or different, each a hydrogen or halogen atom or an alkyl group

and η is an integer from 2 to 5.

130052/0472

The maleimides corresponding to the formula given can be converted in a conventional manner of sharkic anhydride with a polyamine to form a maleic acid amide and subsequent dehydrocyclization of maleic acid amide.

Aromatic amines are preferably used as starting polyamines. The reason for this is to be found in that the desired resin has excellent properties / e.g. B. Heat resistance and the like. Obtained. If the to be made Resin should be pliable and pliable, alicyclic amines can be used alone or in combination with others Amines can be used. Although secondary amines can also be used as starting amines, primary amines are used preferred.

Amines used in the reaction with the cyanate esters to form the cyanate ester copolymers can expediently can also be used as an amine component in the manufacture of maleimides. Besides the mentioned Amines can also be melamine with an s-triazine ring and polyamines obtained by reacting aniline with formaldehyde, in which two or more benzene rings are bonded to one another via a methylene bond, can be used.

The functional maleimides of the type described can be used alone or in a mixture. Further Maleic acid prepolymers can be obtained by heating the maleic acid imide in the presence or absence of a catalyst get used. Finally, copolymers of maleimide and for the synthesis of the polyfunctional maleimide amine used.

130052/0472

A curable resin composition according to the invention is obtained by merely mixing components (a) and (b) or (a), (b) and (c) or by reacting these components beforehand.

As already mentioned, a curable resin composition according to the invention consists of a mixture and / or pre-reaction product from (a) at least one cyanate compound in the form a polyfunctional cyanate ester, a prepolymer of this cyanate ester and / or a copolymer of this Cyanate ester with an amine, with (b) a polyhydantoin resin and optionally (c) at least one maleic acid imide compound in the form of a polyfunctional maleic acid imide, a prepolymer of this maleic acid imide and / or a co-prepolymer of this maleic acid imide with a Amine and also optionally (d) a further component. The resin composition can thus consist of a mixture of the components (a) and (b) and optionally (c) and / or (d), a Pre-reaction product of components (a) and (b), components (a), (b) and (c) or components (a), (b), (c) and (d), a mixture of a pre-reaction product of two or three of components (a), (b), (c) and (d) and the like.

Examples of further components (d) are polyimide resins, epoxy resins, (meth) acrylates, such as methacrylic acid esters, acrylic acid esters, Acrylic alkenyl esters, methacrylic alkenyl esters, methacrylic epoxy esters, acrylic epoxy esters, their prepolymers, Polyallyl compounds, such as diallyl phthalate, divinylbenzene, diallylbenzene, trialkenyl isocyanate or their prepolymers, Phenolic resins, polyvinyl acetal resins, such as polyvinyl formal, polyvinyl acetal or polyvinyl butyral, acrylic resins, Silicone resins or alkyd resins with OH or COOH groups and liquid or elastic rubbers such as polybutadiene, butadiene / acrylonitrile copolymers, Polychloroprene, butadiene / styrene copolymers, polyisoprene, natural rubber,

130052/0472

Polyamide-imide resins, polyester-imide resins, polyester-amide-imide resins and polyparabanic acid.

A curable resin composition according to the invention can be produced well by merely heating to form a cured resin Heat resistance can be crosslinked. To promote the crosslinking reaction of the components used according to the invention however, a curing catalyst is usually used.

Examples of suitable curing catalysts are imidazoles, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-A "thyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, i-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole and addition products of imidazole and trimellitic acid, tertiary amines, such as N, N-dimethylbenzylamine, Ν, Ν-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethyl-p-anisidine, p-halogen-N, N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, Pyridine, quinoline, N-methylmorpholine, triethanolamine, - triethylenediamine, N, N, N; N'-tetramethylbutanediamine, N-methylpiperidine, Phenols such as phenol, cresol, xylenol, resorcinol and phloroglucinol, organic metal salts such as lead naphthenate, Lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, Manganese naphthenate, cobalt naphthenate and acetylacetone iron, inorganic metal salts such as tin (IV) chloride, Zinc chloride and aluminum chloride, peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide and di-tert-butyl diperphthalate, Acid anhydrides, such as maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, Trimellitic anhydride, hexyhydronaphthalic anhydride, Hexahydropyromellitic anhydride and hexahydrotrimellitic anhydride, Azo compounds, such as azoisobutyronitrile, 2,2'-azobispropane or m, m -azoxystyrene, and / or hydrazones or hydrozones.

130052/0472

In addition to the curing catalysts mentioned, curing agents or catalysts for epoxy resins are also suitable.

The amount of catalyst used is less than 5% by weight of the total coating mass.

A curable resin composition according to the invention can be used in a wide variety of ways in order to give it special properties Additives are incorporated as long as they do not impair the essential properties of the (cured) resin. Examples of additives that can be used are fiber reinforcing agents, fillers, pigments, dyes, thickeners, Lubricants, flame retardants and the like.

A curable resin composition according to the invention is available depending on the kind of the components containing it and optionally the pre-reaction conditions are available in a wide variety of forms from liquid to solid at room temperature. Ever According to the intended type of application, they can be in the form of a solid hardenable mass, a liquid hardenable mass or bring a solution of the mass to use.

The curing conditions of a curable resin composition according to the invention depend on the properties and the kind of the constituent components. In general, a resin composition according to the invention can by heating to a temperature of 100 ⁰ C to 250 ⁰ C to cure.

When a curable resin composition according to the invention for the production of moldings, composite structures, with adhesive Unified structures and the like. Is used on the molding, the composite structure or that with adhesive united structures preferably exerted pressure during heat setting. Usually one uses one here Pressure from 981 to 49050 kPa.

A resin composition according to the invention cures rapidly even under mild conditions, so that it is particularly used can be when mass production and easy loading

130052/0472

or processability are desired. One made from a resin mass Cured resin obtained according to the invention has not only excellent adhesion, bonding strength, heat resistance and electrical properties, but also excellent mechanical properties, such as impact strength, Chemical resistance, moisture resistance and the like. A resin composition according to the invention can be obtained in a wide variety of areas of application. Examples of such areas of use are as a coating compound for rust prevention, improvement of flame resistance, flame retardant and the like, as electrical insulating coating, as an adhesive, for composite structures such as those used in furniture production for Building materials, reinforcements, electrically insulating materials and the like. As well as for the manufacture of the most diverse Moldings or moldings.

The following examples or comparative examples are intended to illustrate the invention in more detail. Unless otherwise given, all "%" and "parts" mean "% by weight" and "parts by weight".

example 1

100 g of 2,2-bis (4-cyanatophenyl) propane was at a temperature of 15O ⁰ C (above) allowed to polymerize, and the resulting prepolymer in N, N-dimethylformamide, 450 minutes, and the obtained solution containing 0.05 g Zinc octylate is added.

At the same time, 900 g (solids content) of a commercially available Polyhydantoin resin dissolved in methylene chloride.

130052/0472

After the two solutions prepared as described have been mixed, the solution mixture is reduced to one Applied copper wire and hardened on it by heating. The properties of the coating obtained can be found in the following Table I.

Example 2

A mixture of 920 g of 2,2-bis (4-cyanatophenyl) propane, 64 g of bis (4-maleimidophenyl) methane and 16 g of a mixture of 4-maleimidophenyl-3 ', 4'-dimaleinxmidphenylmethane and 4-maleimidphenyl-2' , 4'-dimaleinimidophenylmethane was (pre) reacted at a temperature of 145 ° C. for 75 minutes. The prepolymer obtained is then introduced into 200 g (solids content) of a commercially available polyhydantoin resin, whereupon the mixture is dissolved in a solvent mixture of methyl ethyl ketone and Ν, Ν-dimethylformamide. After adding 0.4 g of zinc octylate, the solution obtained is applied to a copper wire. The properties of the coating formed can be found in the following Table I.

Comparative experiment 1

For comparison purposes, a polyhydantoin resin solution is applied to copper wire. The properties of this coating can also be found in Table I.

130052/0472

Table I.

ca ο ο σι ro ■> » σ

in methyl ethyl ketone example 1 Example 2 Comparison
example 1 Wire size (in mn) in dimethylf ornamid 1000 1000 1000 Layer thickness (in itm) in N-methyl-2-pyrro-
lidon 0.045 0.041 0.041 Abrasion resistance (number of abrasions
attempts) (back and forth movement, load:
600 g) in methylene chloride 209 250 190 Voltage breakdown Well Well Well Chemical resistance
duration (3-day
total immersion) no changes
change no changes
change no changes
change no changes
change no changes
change weakness
modification no changes
change no changes
change weakness
modification no changes
change no changes
change no changes
change

Example 3

900 g of 2,2-bis (4-cyanatophenyl) ether and 100 g of bis (4-maleinimidphenyl) methane were 90 min allowed to react at a temperature of 15O ⁰ C (in front), and the resulting prepolymer in 200 g (solid content) a commercially available polyhydantoin resin is entered. The mixture obtained is then mixed with 200 g of a commercially available novolak epoxy resin with 0.5 g of zinc octylate, 0.1 pyrocatechol and 0.3 g of triethylenediamine. After uniform grinding and pulverization, the powder obtained is applied to glass fabric by fluidized bed coating and melted with heating, a B-stage prepreg being obtained.

Seven of the sheet prepregs obtained are laid one on top of the other and covered on the top and bottom each with a 35 µm thick copper foil. Thereafter the stack formed is exposed to a molding pressure of 3924 kPa at a temperature of 175 ° C. for 150 minutes, wherein a composite structure clad with copper is obtained. Its physical properties can be found in of the following table II.

Comparative example 2

Example 3 is carried out using the polyhydantoin resin produced a B-stage prepreg alone. When pressing the between two copper foils one Thickness of 35 μπι located stack of seven such Prepregs for 150 minutes at a temperature of 175 ° C. and a pressure of 3924 kPa are not obtained with Copper clad laminate.

130052/0472

Table II

at 25 ⁰ C Example 3 Peel strength of 35 μτη
thick copper foil (kg / cm) at 200 ^° C 1.70 Freezing ^{temperature (0} C) 1.50 Flexural strength in MPa at 25 ⁰ C 251 Chemical resistance
(with 10-hour thawing
chen) at 200 ^° C 706 in 20% HCl 598 In 20% NaOH no change no change

130052/0472

Claims (6)

Claims 2. Composition according to claim 1, characterized in that the cyanate ester of 1,3- or 1,4-dicyanatobenzene, 1,3,5- tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1, 8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis- (4-cyanatophenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatophenyl ) propane, 2,2-bis (3,5-dibromo-4-dicyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4 cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, bis (3-chloro-4-cyanatophenyl) methane, a cyanatonovolak resin derived from a novolak resin and / or · a bisphenol type cyanatopolycarbonate oligomer derived from a bisphenol type polycarbonate oligomer. 3. Composition according to claim 1, characterized in that the weight ratio of component (a) to component (b) 99: 1 to 1:99. 4. Curable resin composition in the form of a mixture and / or a pre-reaction product from Xa) at least one cyanate compound in the form of a polyfunctional cyanate ester, a prepolymer of this cyanate ester and / or a co-prepolymer of this cyanate ester and an amine with (b) a polyhydantoin resin and (c) at least one Ma.leinsäureimidverbindungen in the form of a polyfunctional Maleic acid imide, a prepolymer of this maleic acid imide and / or a co-prepolymer of this maleic acid 130052/0472 acid imides with an amine. 5. Composition according to claim 4, characterized in that the cyanate ester of 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, Bis (4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-dicyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, Bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl ) phosphite, tris (4-cyanatophenyl! phosphate, bis (3-chloro-4-cyanatophenyl) methane, a cyanatonovolak resin derived from a novolak resin and / or one of a bisphenol type cyanatopolycarbonate oligomer derived from a bisphenol type polycarbonate oligomer. 6. Composition according to claim 4, characterized in that the weight ratio of component (a) to component (b) 99: 1 to 1:99. 130052/0472